Azo dyestuffs



Patented Aug. 30, 1938 UNITED STATES PATENT OFFICE on-the-Rhine, BerndEistert,

Mannheim,

and Gustav Klaproth, Ludwigshafen-on-the- Rhine, Germany, assignors toGeneral Aniline Works, Inc., New York, N. Y., a corporation of DelawareNo Drawing. Original application December 18,

.1935, Serial No. 55,040. Divided and this application July 16, 1936,Serial No. 90,944. In Germany December 22, 1934 '7 Claims.

The present invention relates to the production of new azo dyestuffs.This application has been divided out from our copending applicationSer. No. 55,040, filed December 18, 1935.

We have found that new valuable azo dyestuffs are obtained if thecoupling components and the diazo compounds employed in the preparationof the new dyestuffs are so chosen that the molecule of the dyestuficontains at least one sulphonic acid group and at least one basic groupof the general formula in which R1 and R2 may be identical or differentand may be hydrogen or alkyh cycloalkyl, hydroxyalkyl or aralkylradicles or members of a saturated ring system and X is an aliphaticradicle combined with an aromatic nucleus of. the dyestufi moleculeeither directly or by means of a non-basic bridge. As non-basic bridgesmay be mentioned for example -O-, -S-, CO-, SO2--, OCO, --NHCO--,SO2NH-- and -CONH--.

Dyestuffs of the said kind may also be prepared by introducing at leastone basic group of the said general formula into a dyestufi-which doesnot yet contain such a basic group combined in the manner describedabove.

Thus for example a diazotizable amine having the formula:

HmOom-pm-mom).

may be prepared by converting para-nitrophenylethyl alcohol by means ofthionyl chloride into para nitro omega chlorethyl benzene, reacting thelatter with dimethylamine and reducing the nitro group in the resultingamine.

An amine having the formula:

OH: NH:

is obtainable for example by the reaction of metanitroaniline with.chloracetyl chloride, treatment of the resultingchloracetyl-metanitro-anilide with dimethylamine and subsequentreduction of the nitro group.

By the reaction of meta-nitro-omega-chloracetophenone with ethylamineand subsequent reduction of the nitro group, an amine is obtained havingthe formula:

CIHI N From 1-brom-2-(dlethylamino)ethane and para-acetaminothiophenol,a. sulphide is obtained having the formula:

omoo-rvn-O-s-(omh-mcm.

which may be saponified as such to'form the amine or may first beoxidized to form the sulphone having the formula:

omoo-NHOs-onronrmolnm and then saponified.

The amines prepared according to the above methods or by other knownmethods and having external basic groups are capable of diazotization inthe same way as ordinary aromatic amines and yield azo dyestuffs of thesaid kind by coupling with compounds which are capable of coupling.

Coupling components having external basic groups are obtained forexample by reacting 2amino-8-hydroxynaphthalene-6-sulphonic acid withchloracetyl chloride or a chlorpropionic acid chloride and treating theresulting 2-(chloracylamino) 8 hydroxynaphthalene 6 sulphonic acid withpiperidine, dimethylamine or other nitrogen bases which have at leastone reactive hydrogen atom. By reacting 2-acetoxy-3-naphthoio acidchloride with N-diethyl-ethylene- CO-NHGHzCHr-N(C:Ha)i Further suitablecoupling components are for examplejthepyrazolone's'prepared from theabove amines by the usual methods, and also the acetoacetyl orbenzoyl-acetyl and 2-hydroxy-3-naphe. These coupling components may becoupled with any.

thoyl compounds of the said amines.

desired diazotized aromatic amines toyield dyestuffs of the said kind. i

If the coupling component employed contains an amine group, the mono azodyestuff prepared may be diazotized and the diazo- -compound' be coupledwith any desired coupling component. Disazo dyestuffs are thus obtainedwith xcellent properties as regards levelling power and fastness. Theintroduction of the external basicradicle of the general formula /Rl T fi c I B v V V in which X stands ,for an aliphatic radicle into aminoazoor hydroxyazodyestufl's is efiected in a similar manner.

The azo dyestufis obtainable according-to this invention andhavingexternal basic groups are distinguished by an excellent levellingpower and for the most part by good to very good fastness to washing andfulling. When the dyestuffs contain groups which are capable of beingexchanged by metals, they may be converted in substance or on the fibreinto their complex metal com- ,Th l wi g. xample wi l theyillus re e howthe said invention may b'e'f carriedfl out in practice but theinventionis not restricted "to these examples. The parts are by weight.

Exampll 107 parts of para-toluidine are diazotiz ed in the usual mannerand the diazo solution is stirred into a solution, rendered alkalinewith sodium carbonate, of 340' parts of 2-(dimethyl-amino-acetyl) amino-8- hydroxynaphthaleneefi-sulphonic acid, having the formula" thefollowing color shades: V sulphanilic acid Red.:

Aminoazobenzene sulphonic acid;; Bordeaux red. l:.-cmethylj-3- amino.-'6-'chlorben-- 1-;aminonaphthalene. --2- sulphonic c i-..-+fif?-f-r-f' f' e If, instead of "the 2-'(dimethylaminoacetyl) amino*8- hydroxynaphthalene '-6 sulphonic acid the corresponding3,6-disulphonic acid be employed, dyestuffs of similar 'shades'andproperties are obtained. By employing 1- (dimethylaminoacetyl)-amino-8-hydroxynaphthalene-3,6 disulphonic acid, yellower dyestufis arein general obtained.

Example 2 208 parts of p-amino-omega-diethylaminophenetol are diazotizedin the presence of 350 parts of concentrated hydrochloric acid and 1000parts, of water with 69 parts of sodium nitrite. The diazo solution thusobtained is added to an aqiieous solution, containing such an amount ofsodium hydroxide to neutralize the hydrochloric acid; of 213 parts ofthe sodium salt of 1-aminonaphthalne-7sulphonic acid. The mono-azodyestufi thus prepared is salted out, separated, @dissolved" again underthe addition of acid and dia'zoti zedwith sodium nitrite. The diazosolution thus'obtained is added to an aqueous solution, containing suchan amount of sodium acetate to-n'eutralize the'acid,'of 289 parts of thesodium salt off :l-phenylaminonaphthalene-8-sulphonic ,facid. disazodyestuff is thus obtained which dyes wool beautiful blue shades of goodfastness to washing and -fulling.

Instead of para-aminoromega-diethylaminophenetol other amines"containing external basic l'q lpsmay beemployed. As amines of this kindthere may be mentioned iraminobenzyl-dimethyl amine, 3 amino 4methylphenyl l omega (dimeth ylamino'ethyl) sulphone, 3,- amin'omethoxyphenyl e omega dimethylamino ethyl) -sulphone or thecorresponding di ethylcompounds. Instead of l amino-naphthaleneflsulphonic acid there may also. be employedas :the first couplingcomponent l-aminonaphthalenegfisulphonic acid or a mixture of these twoacids. Instead of 1 phenylamino naphthalene -8- sulphonic acid there maybe employed as the second coupling component, the LOP-methylphenyl)-aminonaphthalene-8 sulphonic acid. If. the amineused for-thepreparationot-the diazo component already contains a sulphonic acid;group;v 1- -amino'-naphthalene maybe -em ployed'as the first couplingcomponent in this case V Whatwe claim is:-: e

:1. Azo' dyestufis corresponding to the general formulae" T wherein' Arstan'dsfor an aromatic radical; the

stands for 5. basic radical selected from the group consisting of -NH2,primary and secondary alkyl, hyd'rox'y'alkyl,

v aralkyl and cycloalkyl amino groups and the radicals of hydrogenatedheterocyclic nitrogen compounds includingthe N atom, X stands for achaincontaining carbon atoms, which is free from; a basic action, and, Bstands for the radicle of an aromatic a'zo compound, andin which atleast one of the radicles marked Ar and B contains a sulphonicacid'group.

2. A20 dyestuifs corresponding to the general formula V B'N=NAr--XN .Y

wherein Ar stands for an aromatic radical, the group stands for a basicradical selected from the group consisting of -NI-I2, primary andsecondary alkyl, hydroxyalkyl, aralkyl and cycloalkyl amino groups andthe radicals of hydrogenated heterocyclic nitrogen compounds includingthe N atom, X stands for a chain containing carbon atoms, which is freefrom a basic action, and, B stands CaHs for a radicle corresponding tothe general formula:

HRN OH in which the nucleus marked A contains at least one substituentof the class consisting of halogen atoms and nitro groups.

3. The azo dyestufif corresponding to the formula which is free from abasic action, and, B stands for a radicle corresponding to the generalformula in which at least one of the naphthalene nuclei I and 11contains at least one sulphonic acid group and in which R3 stands forhydrogen or a radicle of the benzene series.

5. The azo dyestuff corresponding to the formula N=NOO CHzCHiN CzHs 6.Azo dyestufis corresponding to the general formula wherein Ar stands foran aromatic radical, the

group R: stands for a basic radical selected from thegroup GEN o o CaHnHm OH 1 S-CHaCHzN olN N=N /N=N 1103s \SO3H 4. A20 dyestuffscorresponding to the general formula BN=N--AIXN wherein Ar stands for anaromatic radical, the group stands for a basic radical selected from thegroup consisting of -NI-I2, primary and secondary alkyl,

HO:S

hydroxyalkyl, aralkyl and cycloalkyl amino groups and the radicals ofhydrogenated heterocyclic nitrogen compounds including the N atom, Xstands for a chain containing carbon atoms,

formula s-cmonm /N=N if 11101 SOzH H 11 HANS KRZIKALLA. HANNS UFER. IBERN'D EISTERT.

GUSTAV KLAPRO'I'H.

